EP1975160B1 - Polymerisierbare Verbindung, Polymer, Tintenzusammensetzung, gedruckte Artikel und Tintenstrahlaufzeichnungsverfahren - Google Patents

Polymerisierbare Verbindung, Polymer, Tintenzusammensetzung, gedruckte Artikel und Tintenstrahlaufzeichnungsverfahren Download PDF

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Publication number
EP1975160B1
EP1975160B1 EP20080005793 EP08005793A EP1975160B1 EP 1975160 B1 EP1975160 B1 EP 1975160B1 EP 20080005793 EP20080005793 EP 20080005793 EP 08005793 A EP08005793 A EP 08005793A EP 1975160 B1 EP1975160 B1 EP 1975160B1
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EP
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Prior art keywords
group
meth
ink composition
pigment
acrylate
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EP20080005793
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English (en)
French (fr)
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EP1975160A1 (de
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Norihide Shimohara
Hisato Nagase
Shigetomo Tsujihata
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Fujifilm Corp
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Fujifilm Corp
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D221/00—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00
    • C07D221/02—Heterocyclic compounds containing six-membered rings having one nitrogen atom as the only ring hetero atom, not provided for by groups C07D211/00 - C07D219/00 condensed with carbocyclic rings or ring systems
    • C07D221/04—Ortho- or peri-condensed ring systems
    • C07D221/06—Ring systems of three rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/06—Peri-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/12—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains three hetero rings
    • C07D471/16—Peri-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
    • C09D11/00—Inks
    • C09D11/02—Printing inks
    • C09D11/10—Printing inks based on artificial resins
    • C09D11/101—Inks specially adapted for printing processes involving curing by wave energy or particle radiation, e.g. with UV-curing following the printing

Definitions

  • the present invention relates to an ink composition comprising a polymerizable compound and a polymer.
  • the present invention relates to an ink composition comprising a polymerizable compound that is very useful industrially.
  • the present invention in particular relates to an ink composition suitably used for inkjet recording, a printed article using the ink composition, and an inkjet recording method using the ink composition.
  • the present invention relates to: an ink composition suitable for inkjet recording, the ink composition being superior in the dispersibility of a colorant so that it has excellent coloring property, being cured by irradiation with an active radiation ray without generating volatile components and enabling the formation of a high quality image; a printed article obtained using the ink composition, and an inkjet recording method using the ink composition.
  • an image recording method for forming an image on a recording medium such as paper based on image data signals
  • a recording medium such as paper based on image data signals
  • an electrophotographic system there are an electrophotographic system, sublimation-type and melt-type thermal transfer systems, an inkjet system, etc.
  • the inkjet system is applicable to an inexpensive apparatus, and performs direct image formation on a recording medium by ejecting ink only to image areas where ink deposition is necessary; therefore, the inkjet system uses ink effectively, thus reducing the running cost. Further, the inkjet system generates less noise and is a superior image recording system.
  • the inkjet system enables printing on recording media that do not absorb water, such as plastic sheets and metallic plates, as well as on paper.
  • an inkjet recording ink that can be cured by irradiation with an active radiation ray is used.
  • sharp images can be formed by curing ink droplets by irradiation with an active radiation ray immediately after printing.
  • the curable ink composition in such an inkjet recording ink that can be cured is required to have high dispersibility of a pigment, and stability over time.
  • Reduction in the pigment size is necessary for imparting clear tone and high tinting strength to the ink composition.
  • ejected droplets of the inkjet ink exert a significant influence on the sharpness of images; therefore, the ejection quantity of the ink droplets needs to be small, and the size of the pigment particles contained in the ink has to be smaller than the thickness of the film formed by curing of the ink.
  • the size of the pigment particles is reduced so as to achieve higher tinting strength, the pigment particles are hard to disperse, and pigment aggregates are easily formed.
  • Another problem is created in that the viscosity of the ink composition is increased by the addition of a dispersant.
  • the formation of the pigment aggregates and the increase in the viscosity of the ink composition both adversely affect ink ejection property, and such an ink composition is not preferred.
  • the ink composition When an ink composition is used in inkjet recording, the ink composition is contained in a cartridge.
  • the ink composition in the cartridge is heated at ejection and cooled at a non-ejection time and at storage; in this way, the ink composition undergoes repeated temperature changes (heating-cooling).
  • This temperature changes also adversely affect the pigment dispersibility, and the pigment dispersibility is deteriorated with time, causing problems that pigment aggregates are easily formed, or the increase in the viscosity of the ink composition easily occurs.
  • an ink composition using a pigment derivative as a dispersant (see, for example, Japanese Patent Application Laid-Open (JP-A) Nos. 2003-119414 and 2004-18656 ); an ink composition that uses a polymer having a basic group as a dispersant for a specific pigment such as a phthalocyanine-based or quinacridone-based pigment (see, for example, JP-A No. 2003-321628 ); and an ink composition which is free of organic solvent and contains a dispersant such as poly(ethyleneimine)-poly(12-hydroxystearic acid) graft polymer and a specific monomer that dissolves the dispersant (see, for example, JP-A No. 2004-131589 ) have been proposed.
  • JP-A Japanese Patent Application Laid-Open
  • the dispersion stability of pigments is actually improved owing to the function of the dispersant.
  • the size of the pigment used in the ink composition is not sufficiently small, and there is a room for improvement of dispersibility of finer pigment particles.
  • the ink composition also has a problem in that the dispersion stability upon long-term storage or upon repeated temperature changes is still insufficient.
  • an object of the present invention is to solve the conventional problems and to achieve the following objects. Specifically, an object of the present invention is to provide an ink composition suitable for inkjet recording, which can form a high quality image with clear tone and high tinting strength and can be cured by irradiation with an active radiation ray without generating volatile components, a printed article obtained using the ink composition, and ( an inkjet recording method using the ink composition.
  • the present invention can solve the conventional problems and can achieve the above object.
  • the present invention can provide an ink composition suitable for inkjet recording which is superior in the dispersibility of fine pigments and in the stability of the dispersion, enables the formation of a high quality image having a sharp color tone and high tinting strength, and can be cured by irradiation with an active radiation ray.
  • the present invention can provide a printed article with a high quality image which was obtained using the ink composition that can be cured by irradiation with an active radiation ray and provide a sharp color tone and high tinting strength.
  • the polymerizable compound that is comprised in the ink composition of the present invention is represented by the following formula (1).
  • R 1 represents a hydrogen atom, or a substituted or unsubstituted alkyl group.
  • the alkyl group has preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 4 carbon atoms.
  • Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, an i-butyl group, a t-butyl group, an n-hexyl group, a cyclohexyl group, a 2-hydroxyethyl group, a 3-hydroxypropyl group, a 2-hydroxypropyl group, and a 2-methoxyethyl group.
  • R 2 represents an alkylene group and has preferably 1 to 12 carbon atoms, more preferably 1 to 8 carbon atoms, still more preferably 1 to 4 carbon atoms.
  • alkylene group include a methylene group, an ethylene group, a propylene group, a trimethylene group, and a tetramethylene group.
  • n each independently represent 0 or 1.
  • R 3 and R 4 may each represent an optionally present monovalent substituent.
  • the optionally present monovalent substituent for R 3 or R 4 is preferably an alkyl group, an aryl group, a halogen atom, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an alkoxycarbonyl group, an acylamino group, a carbamoyl group, a cyano group, an alkylsulfonyl group, an arylsulfonyl group, an acyl group, or a sulfamoyl group, and more preferably, a halogen atom, an alkyl group, an aryl group, an alkoxy group, an aryloxy group, an alkylthio group, an arylthio group, an acylamino group, or a sulfonylamino group.
  • the substituent represented by R 3 or R 4 may be unsubstituted or substituted.
  • an alkyl group, an aryl group, a halogen atom, an alkoxy group, an aryloxy group, an alkoxycarbonyl group, an acyloxy group, an acylamino group, a carbamoyl group, a cyano group, a carboxyl group, a sulfonyl group, and a heterocyclic residue are preferable.
  • the alkyl group for R 3 or R 4 is preferably an alkyl group having 1 to 30 total carbon atoms, more preferably, an alkyl group having 1 to 20 total carbon atoms. Specifically, a methyl group, an ethyl group, a butyl group, a hexyl group, an octyl group, a 2-ethylhexyl group, a 3,5,5-trimethylhexyl group, a dodecyl group, an octadecyl group, a benzyl group, a (4-ethoxyphenyl) methyl group, an N,N-diethyl carbamoyl methyl group, an N,N-dibutyl carbamoyl methyl group, a 1-(N,N-dibutyl carbamoyl) ethyl group, a 2-methoxy ethyl group, a 1-methyl-2-phenoxyethyl group, a (4
  • the aryl group for R 3 or R 4 is preferably an aryl group having 6 to 30 total carbon atoms, more preferably, an aryl group having 1 to 20 total carbon atoms.
  • a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group, a 4-methylphenyl group, a 4-phenylphenoxy group, a 4-chlorophenyl group, a 2-methoxyphenyl group, a 3-ethoxyphenyl group, a 4-butoxyphenyl group, a 2,4-diethoxyphenyl group, a 2,5-dibutoxyphenyl group, a 4-phenoxyphenyl group, a naphthyl group, a 4-dibutyl carbamoyl phenyl group and a 4-dibutyl sulfamoyl phenyl group are preferable, and a phenyl group, a 2-methylphenyl group, a 3-methylphenyl group
  • the halogen atom for R 3 or R 4 is preferably a fluorine atom, a chlorine atom, a bromine atom or an iodine atom, and more preferably a fluorine atom or a chlorine atom.
  • the alkoxy group for R 3 or R 4 is preferably an alkoxy group having 1 to 30 total carbon atoms, more preferably, an alkoxy group having 1 to 20 total carbon atoms.
  • a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a hexyloxy group, a 2-ethylhexyloxy group, a 3,5,5-trimethyl hexyloxy group, an octyloxy group, a decyloxy group, a 2-phenoxyethoxy group, a 2-(3,5-di-t-butylphenoxy) ethoxy group, a dibutyl carbamoyl methoxy group, a hexadecyloxy group and an octadecyloxy group are preferable, and a methoxy group, an ethoxy group, a butoxy group, a hexyloxy group, a 2-ethyl
  • the aryloxy group for R 3 or R 4 is preferably an aryloxy group having 6 to 30 total carbon atoms, more preferably, an aryloxy group having 6 to 20 total carbon atoms.
  • a phenoxy group, a tolyloxy group, a 4-chlorophenyloxy group, a 4-acetamide phenyloxy group, a 2-butoxyphenyloxy group, a 2-benzoyl aminophenyloxy group, a 2,5-dimethoxy-4-nitrophenyloxy group and a 3-octyloxy phenyloxy group are preferable, and a phenoxy group, a tolyloxy group, a 4-chlorophenyloxy group, a 4-acetamide phenyloxy group, a 2-butoxyphenyloxy group and a 2,5-dimethoxy-4-nitrophenyloxy group are more preferable.
  • the alkylthio group for R 3 or R 4 is preferably an alkylthio group having 1 to 30 total carbon atoms, more preferably, an alkylthio group having 1 to 20 total carbon atoms.
  • the arylthio group for R 3 or R 4 is preferably an arylthio group having 6 to 30 total carbon atoms, more preferably, an arylthio group having 6 to 20 total carbon atoms.
  • a phenylthio group, a tolylthio group, a 4-chlorophenylthio group, a 4-acetamide phenylthio group, a 2-butoxyphenylthio group, a 2-benzoyl aminophenylthio group, a 2,5-dimethoxy-4-nitrophenylthio group, a 3-octyloxy phenylthio group are preferable, and a phenylthio group, a tolylthio group, a 4-chlorophenylthio group, a 4-acetamide phenylthio group, a 2-butoxyphenylthio group and a 2,5-dimethoxy-4-nitrophenylthio group are more preferable.
  • the alkoxycarbonyl group for R 3 or R 4 is preferably an alkoxycarbonyl group having 2 to 30 total carbon atoms, more preferably, an alkoxycarbonyl group having 2 to 20 total carbon atoms.
  • a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group, a phenoxycarbonyl group, a (2-ethylhexyl) oxycarbonyl group, a hexyloxycarbonyl group, an octyloxycarbonyl group, a (4-methoxyphenyl) oxycarbonyl group are preferable, and a methoxycarbonyl group, an ethoxycarbonyl group, a butoxycarbonyl group and a phenoxycarbonyl group are more preferable.
  • the acylamino group for R 3 or R 4 is preferably an acylamino group having 1 to 30 total carbon atoms, more preferably, an acylamino group having 1 to 20 total carbon atoms.
  • a formylamino group, an acetylamino group, a butyrylamino group, a lauroylamino group, a benzoylamino group, a toluoylamino group, a phenoxyacetyl group, a (4-methoxyphenoxy)acetyl group, a 2',4'-dichlorobenzoylamino group, a 2',4'-di-t-amylbenzoylamino group, an acetylmethylamino group, a benzoylmethylamino group and an acetylbenzylamino group are preferable, and an acetylamino group, a butyrylamino group, a be
  • the carbamoyl group for R 3 or R 4 is preferably a carbamoyl group having 1 to 30 total carbon atoms, more preferably, a carbamoyl group having 1 to 20 total carbon atoms.
  • the alkylsulfonyl group for R 3 or R 4 is preferably an alkylsulfonyl group having 1 to 30 total carbon atoms, more preferably, an alkylsulfonyl group having 1 to 20 total carbon atoms.
  • a methylsulfonyl group, an ethylsulfonyl group, a butylsulfonyl group, a hexylsulfonyl group and a benzylsulfonyl group are preferable, and a methylsulfonyl group and a benzylsulfonyl group are more preferable.
  • the arylsulfonyl group for R 3 or R 4 is preferably an arylsulfonyl group having 1 to 30 total carbon atoms, more preferably, an arylsulfonyl group having 1 to 20 total carbon atoms.
  • a phenylsulfonyl group, a 4-methylphenylsulfonyl group, a naphthylsulfonyl group, a 4-methoxysulfonyl group and a 4-chlorophenyl sulfonylgroup are preferable, and a methyl sulfonyl group, a phenyl sulfonyl group and a 4-methylphenyl sulfonyl group are more preferable.
  • the acyl group for R 3 or R 4 is preferably an acyl group having 1 to 30 total carbon atoms, more preferably, an acyl group having 1 to 20 total carbon atoms.
  • a formyl group, an acetyl group, a propionyl group, a pivaloyl group, a butyloyl group, a 4-phenoxy butyloyl group, a benzoyl group, a (4-ethoxyphenyl) carbonyl group, a (2-buthoxyphenyl) carbonyl group and a (4-chlorophenyl) carbonyl group are preferable, and a formyl group, an acetyl group, a propionyl group, a pivaloyl group, a benzoyl group and a (4-chlorophenyl) carbonyl group are more preferable.
  • the sulfamoyl group for R 3 or R 4 is preferably a sulfamoyl group having 1 to 30 total carbon atoms, more preferably, a sulfamoyl group having 1 to 20 total carbon atoms.
  • a sulfamoyl group, an N-phenyl sulfamoyl group, an N,N-dimethyl sulfamoyl group, an N,N-diethyl sulfamoyl group, an N,N-dibutyl sulfamoyl group, an N,N-dihexyl sulfamoyl group, an N,N-diphenyl sulfamoyl group, an N-methyl-N-phenyl sulfamoyl group, an N-ethyl-N-phenyl sulfamoyl group, an N-methyl-N-tolyl sulfamoyl group, a morpholino sulfonyl group, a piperidino sulfonyl group and an N,N-bis (2-methoxyethyl) sulfonyl group are preferable, and a morpholino
  • the polymerizable compound is preferably represented by the following formula (2).
  • R 3 and R 4 may each represent an optionally present monovalent substituent.
  • Preferable examples of the substituent are the same as those described above in formula (1).
  • the polymer of the present invention is a polymer that comprises a copolymer unit derived from the polymerizable compound (monomer) represented by the above formula (1) or formula (2).
  • the polymer is preferably a graft copolymer that contains, as a copolymer unit, a polymerizable oligomer having an ethylenically unsaturated double bond at its terminal.
  • Such a polymerizable oligomer having an ethylenically unsaturated double bond at its terminal is a compound having a given molecular mass and is therefore called a macromonomer.
  • the polymerizable oligomer contains a polymer chain moiety and a polymerizable functional group moiety at a terminal of the polymer chain.
  • the polymerizable functional group moiety has an ethylenically unsaturated double bond.
  • the group having an ethylenically unsaturated double bond is preferably present at only one of the terminals of the polymer chain.
  • the group having an ethylenically unsaturated double bond is preferably a (meth)acryloyl group or a vinyl group, and more preferably a (meth)acryloyl group.
  • the polystyrene-equivalent number-average molecular mass (Mn) of the macromonomer is preferably in the range of 1,000 to 10,000, more preferably in the range of 2,000 to 9,000.
  • the polymer chain moiety is generally a homopolymer or copolymer formed from at least one monomer selected from the group consisting of alkyl (meth)acrylates, styrene and derivatives thereof, acrylonitrile, vinyl acetate, and butadiene, or is polyethylene oxide, polypropylene oxide, and polycaprolactone.
  • the polymerizable oligomer is preferably an oligomer represented by the following formula (3).
  • R 11 and R 13 each independently represent a hydrogen atom or a methyl group.
  • R 12 represents an alkylene group having 1 to 12 carbon atoms (preferably an alkylene group having 2 to 4 carbon atoms, may have a substituent (for example, a hydroxyl group) and may be bound to each other via e.g. an ester bond, ether bond or amide bond).
  • Y represents a phenyl group, a phenyl group with an alkyl group having 1 to 4 carbon atoms, or -COOR 14 (where R 14 represents an alkyl group having 1 to 6 carbon atoms, a phenyl group, or an arylalkyl group having 7 to 10 carbon atoms), and q is from 20 to 200.
  • Y is preferably a phenyl group or -COOR 14 (where R 14 is an alkyl group having 1 to 12 carbon atoms.).
  • polymerizable oligomer examples include polymers in which a (meth)acryloyl group is bound to one terminal of polymethyl (meth)acrylate, poly-n-butyl (meth)acrylate, poly-i-butyl (meth)acrylate or polystyrene.
  • the polymerizable oligomer may be not only polymerizable oligomers represented by the formula (3) but also polymerizable oligomers represented by the following formula (4).
  • R 21 represents a hydrogen atom or a methyl group
  • R 22 represents an alkylene group having 1 to 8 carbon atoms
  • X 21 represents -OR 23 or -OCOR 24 , where R 23 and R 24 represent a hydrogen atom, an alkyl group or an aryl group.
  • n denotes a number from 2 to 200.
  • R 21 represents a hydrogen atom or a methyl group.
  • R 22 represents an alkylene group having 1 to 8 carbon atoms, is preferably an alkylene group having 1 to 6 carbon atoms and is more preferably an alkylene group having 2 to 3 carbon atoms.
  • X 21 represents -OR 23 or -OCOR 24 , where R 23 represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, a phenyl group or a phenyl group substituted with an alkyl group having 1 to 18 carbon atoms.
  • R 24 represents an alkyl group having 1 to 18 carbon atoms.
  • n denotes a number 2 to 200, preferably 5 to 100 and more preferably 10 to 100.
  • Examples of the polymerizable oligomer represented by the formula (4) include polyethylene glycol mono(meth)acrylate, polypropylene glycol mono(meth)acrylate, polyethylene glycol polypropylene glycol mono(meth)acrylate and polytetramethylene glycol monomethacrylate. These materials may be commercially available products or may be those synthesized properly.
  • the polymerizable monomers represented by the formula (4) are commercially available. Examples of these commercially available products include methoxypolyethylene glycol methacrylate (trade name: NK ESTER M-40G, M-90G and M-230G (manufactured by Toagosei Co., Ltd.); trade name: BLENMER-PME-100, PME-200, PME-400, PME-1000, PME-2000 and PME-4000 (manufactured by NOF CORPORATION)), polyethylene glycol monomethacrylate (trade name: BLENMER-PE-90, PE-200 and PE-350, manufactured by NOF CORPORATION), polypropylene glycol monomethacrylate (trade name: BLENMER-PP-500, PP-800 and PP-1000, manufactured by NOF CORPORATION), polyethylene glycol polypropylene glycol monomethacrylate (trade name: BLENMER-70PEP-370B, manufactured by NOF CORPORATION), polyethylene
  • the polymer for use in the present invention may be a copolymer with a monomer having a nitrogen atom.
  • the monomer having a nitrogen atom include N,N-dimethylaminoethyl(meth)acrylate, N,N-dimethylaminopropyl(meth)acrylate, 1-(N,N-dimethylamino)-1,1-dimethylmethyl(meth)acrylate, N,N-dimethylaminohexyl(meth)acrylate, N,N-diethylaminoethyl(meth)acrylate, N,N-diisopropylaminoethyl(meth)acrylate, N,N-di-n-butylaminoethyl(meth)acrylate, N,N-di-i-butylaminoethyl(meth)acrylate, morpholinoethyl(meth)acrylate, piperidinoethyl(meth)acryl
  • N,N-dimethylaminoethyl(meth)acrylate, N,N-dimethylaminopropyl(meth)acrylate, 3-(N,N-diethylamino)propyl(meth)acrylamide, 3-(N,N-dimethylamino)propyl(meth)acrylamide, 2-vinylpyridine, 4-vinylpyridine, and N-vinylimidazole are preferable.
  • the polymer for use in the present invention may be a copolymer with other monomers copolymerizable with these polymers.
  • the other monomers copolymerizable with these polymers may include unsaturated carboxylic acids (for example, (meth)acrylic acids, crotonic acid, itaconic acid, maleic acid and fumaric acid), aromatic vinyl compounds (for example, styrene, ⁇ -methylstyrene, vinyltoluene, 2-vinylpyridine, 4-vinylpyridine and N-vinylimidazole), alkyl(meth)acrylates (for example, methyl(meth)acrylate, ethyl(meth)acrylate, n-butyl(meth)acrylate and i-butyl(meth)acrylate), alkylaryl(meth)acrylates (for example, benzyl(meth)acrylate), substituted alkyl(meth)acrylates (for example, glycidyl(me
  • the polymer of the present invention is preferably a copolymer that comprises a copolymer unit derived from the polymerizable compound represented by the above formula (1) or (2) and a repeating unit given from the polymerizable oligomer (macromonomer), or a copolymer that comprises a repeating unit represented by the above formula (1), a repeating unit given from the polymerizable oligomer (macromonomer) and a repeating unit given from a monomer having a nitrogen atom.
  • the above copolymer preferably contains the repeating unit represented by the formula (1) in a ratio 5% by weight to 70% by weight (particularly, 5% by weight to 30% by weight) based on all repeating units.
  • the above copolymer preferably contains the repeating unit given from the polymerizable oligomer (macromonomer) in a ratio 30% by weight to 95% by weight (particularly, 50% by weight to 90% by weight) based on all repeating units.
  • the above copolymer preferably contains the repeating unit derived from the above monomer containing nitrogen containing group in a ratio 5% by weight to 80% by weight (particularly, 5% by weight to 50% by weight) based on all repeating units.
  • the quantity of the repeating units derived from the additional monomer is preferably in the range of 5% by weight to 30% by weight based on the total quantity of the repeating units in the copolymer.
  • the weight-average molecular mass (Mw) of the copolymer is preferably in the range of 1,000 to 200,000, more preferably in the range of 10,000 to 100,000. This weight-average molecular mass is a polystyrene equivalent weight-average molecular mass determined by gel permeation chromatography (carrier: tetrahydrofuran).
  • the structure of the copolymer can be analyzed, for example, by performing 1H-NMR measurement (a measurement using Mercury (300 MHz) manufactured by Varian, Inc.).
  • graft copolymer examples of the graft copolymer that can be suitably used for the polymer of the present invention will be shown below; however, these examples are not intended to limit the present invention.
  • Such graft copolymers can be obtained by radical polymerization, in a solvent, of the polymerizable oligomer and, optionally, the monomer having a nitrogen-containing group and/ or other additional monomers.
  • a radical polymerization initiator is used in general.
  • a chain transfer agent e.g., 2-mercaptoethanol and dodecyl mercaptan
  • the ink composition of the present invention comprises, in addition to the polymer, at least (a) other polymerizable compound and (b) a pigment, and may comprise other components as necessary.
  • the polymers may be used alone, or two or more may be used in combination.
  • the content of the polymer in the ink composition is preferably 1% by mass to 100% by mass, more preferably 5% by mass to 50% by mass based on the amount of pigment to be added.
  • a known pigment dispersant may be used together in addition to the polymer insofar as the effect of the present invention is not impaired.
  • the amount of the known pigment dispersant to be added is preferably 50% by mass or less based on the polymer.
  • the polymer is used as a pigment dispersant.
  • the structure having high affinity to a pigment due to a van-der-waals interaction ensures good adsorbing ability with respect to the pigment, making it possible to obtain a stable dispersant. Since the polymer is a high-molecular compound having a specified repeating structure, the steric repulsive effect of a high-molecular chain enables high dispersion stability.
  • the pigment include organic pigments such as a phthalocyanine base, insoluble azo base, azo lake base, anthraquinone base, quinacridone base, dioxazine base, diketopyrrolopyrrole base, anthrapyrimidine base, anthanthrone base, indanthrone base, flavanthrone base, perinone base, perylene base, thioindigo base and quinophthalone base.
  • organic pigments such as a phthalocyanine base, insoluble azo base, azo lake base, anthraquinone base, quinacridone base, dioxazine base, diketopyrrolopyrrole base, anthrapyrimidine base, anthanthrone base, indanthrone base, flavanthrone base, perinone base, perylene base, thioindigo base and quinophthalone base.
  • the ink composition of the present invention is cured through the function of other polymerizable compound (a) when some energy is applied thereto.
  • the ink composition of the present invention contains (c) a polymerization initiator and is cured by irradiation with an active energy ray.
  • the active energy ray is not particularly limited as long as it can impart energy which can generate initiating species in the ink composition by irradiation therewith.
  • the energy ray include a wide range of energy rays such as ⁇ -rays, ⁇ -rays, X-rays, ultraviolet rays, visible rays and electron rays.
  • the ink composition of the present invention is preferably an ink composition which can be cured by irradiation with ultraviolet rays as the radiation ray.
  • the curable ink composition of the present invention comprises other polymerizable compound (a).
  • Any polymerizable compound may be used as the other polymerizable compound (a) without any particular limitation as long as it causes a polymerization reaction and is cured by supplying some energy.
  • any of a monomer, oligomer and polymer may be used, in particular, various known polymerizable monomers known as a photo-cationic polymerizable monomer or photo-radical polymerizable monomer are preferable which causes a polymerization reaction by initiator species generated from the polymerization initiator (c) which is added as desired.
  • the polymerizable compounds may be used alone or two or more may be used in combination with the intention of adjusting, for example, reaction speed, ink properties and the properties of a cured film. Also, the polymerizable compounds may be either a monofunctional compound or a multifunctional compound.
  • Examples of cation-polymerizable monomers that can be used as the other polymerizable compound (a) include the epoxy compounds, vinyl ether compounds, and oxetane compounds described in JP-A Nos. 6-9714 , 2001-31892 , 2001-40068 , 2001-55507 , 2001-310938 , 2001-310937 and 2001-220526 .
  • Examples of monofunctional epoxy compounds that can be used as the cation-polymerizable monomer include phenyl glycidyl ether, p-tert-butylphenyl glycidyl ether, butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, 1,2-butylene oxide, 1,3-butadiene monoxide, 1,2-epoxydodecane, epichlorohydrin, 1,2-epoxydecane, styrene oxide, cyclohexene oxide, 3-methacryloyloxymethylcyclohexene oxide, 3-acryloyloxymethylcyclohexene oxide, and 3-vinylcyclohexene oxide.
  • aromatic epoxides and alicyclic epoxides are preferable since they are advantageous in respect of the curing rate, alicyclic epoxides are more preferable.
  • Examples of monofunctional vinyl ether compounds that can be used as the cation-polymerizable monomer include methyl vinyl ether, ethyl vinyl ether, propyl vinyl ether, n-butyl vinyl ether, t-butyl vinyl ether, 2-ethylhexyl vinyl ether, n-nonyl vinyl ether, lauryl vinyl ether, cyclohexyl vinyl ether, cyclohexyl methyl vinyl ether, 4-methylcyclohexylmethyl vinyl ether, benzyl vinyl ether, dicyclopentenyl vinyl ether, 2-dicyclopentenoxy ethyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, butoxyethyl vinyl ether, methoxyethoxyethyl vinyl ether, ethoxyethoxyethyl vinyl ether, methoxy polyethylene glycol vinyl ether, tetrahydrofurfuryl vinyl
  • a di- or trivinyl ether compound is preferable from the viewpoint of curing properties, adhesion to a recording medium, and the surface hardness of an image formed, and a divinyl ether compound is particularly preferable.
  • the oxetane compound that can be used as the cation-polymerizable monomer refers to a compound having an oxetane ring.
  • Such an oxetane compound may be selected arbitrarily from known oxetane compounds, for example, those described in JP-A Nos. 2001-220526 , 2001-310937 , and 2003-341217 .
  • the compound having an oxetane ring is preferably a compound having 1 to 4 oxetane rings in its structure.
  • Examples of monofunctional oxetanes that can be used as the cation-polymerizable monomer include 3-ethyl-3-hydroxymethyl oxetane, 3-(meth)allyloxymethyl-3-ethyl oxetane, (3-ethyl-3-oxetanylmethoxy)methyl benzene, 4-fluoro-[1-(3-ethyl-3-oxetanylmethoxy)methyl] benzene, 4-methoxy-[1-(3-ethyl-3-oxetanylmethoxy)methyl] benzene, [1-(3-ethyl-3-oxetanylmethoxy)ethyl]phenyl ether, isobutoxymethyl(3-ethyl-3-oxetanylmethyl) ether, isobornyloxyethyl(3-ethyl-3-oxetanylmethyl) ether, isobornyl
  • Examples of multifunctional oxetanes that can be used as the cation-polymerizable monomer include 3,7-bis(3-oxetanyl)-5-oxa-nonane, 3,3'-(1,3-(2-methylenyl) propanediylbis (oxymethylene)) bis-(3-ethyloxetane), 1,4-bis[(3-ethyl-3-oxetanylmethoxy)methyl] benzene, 1,2-bis[(3-ethyl-3-oxetanylmethoxy)methyl] ethane, 1,3-bis[(3-ethyl-3-oxetanylmethoxy)methyl] propane, ethylene glycol bis(3-ethyl-3-oxetanylmethyl) ether, dicyclopentenyl bis(3-ethyl-3-oxetanylmethyl) ether, triethylene glycol bis(3-ethyl-3-oxet
  • oxetane compounds as the cation-polymerizable monomer, a compound having one or two oxetane rings is preferable from the viewpoint of the viscosity and adhesiveness of the ink composition.
  • the ink composition of the present invention as a cation-polymerizable monomer, only one compound may be used, or two or more compounds may be used in combination. From the viewpoint of effective suppression of shrinkage upon curing, it is preferable to use a combination of at least one oxetane compound and at least one compound selected from epoxy compounds and vinyl ether compounds.
  • the other polymerizable compound (a) may be selected from a wide variety of known radical polymerizable monomers that undergo polymerization reaction in the presence of an initiator species generated from a photoradical initiator.
  • radical polymerizable monomers examples include (meth)acrylates, (meth)acrylamides, and aromatic vinyls.
  • (meth)acrylate is occasionally used to mean “acrylate” and/ or “methacrylate”
  • (meth)acryl is occasionally used to mean “acryl” and/or "methacryl”.
  • Examples of (meth)acrylates that can be used as the radical polymerizable monomer include monofunctional (meth)acrylates, bifunctional (meth)acrylates, trifunctional (meth)acrylates, tetrafunctional (meth)acrylates, pentafunctional (meth)acrylates, and hexafunctional (meth)acrylates.
  • Examples of monofunctional (meth)acrylates include hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, tert-octyl (meth)acrylate, isoamyl (meth)acrylate, decyl (meth)acrylate, isodecyl (meth)acrylate, stearyl (meth)acrylate, isostearyl (meth)acrylate, cyclohexyl (meth)acrylate, 4-n-butylcyclohexyl (meth)acrylate, bornyl (meth)acrylate, isobornyl (meth)acrylate, benzyl (meth)acrylate, 2-ethylhexyldiglycol (meth)acrylate, butoxyethyl (meth)acrylate, 2-chloroethyl (meth)acrylate, 4-bromobutyl (meth)acrylate, cyanoethyl (meth)acrylate
  • bifunctional (meth)acrylates include 1,6-hexanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 2,4-dimethyl-1,5-pentanediol di(meth)acrylate, butylethylpropanediol (meth)acrylate, ethoxylated cyclohexane methanol di(meth)acrylate, polyethylene glycol di(meth)acrylate, oligoethylene glycol di(meth)acrylate, ethylene glycol di(meth)acrylate, 2-ethyl-2-butyl-butanediol di(meth)acrylate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, EO-modified bisphenol A di(meth)acrylate, bisphenol F polyethoxy di(meth)acrylate, polypropy
  • trifunctional (meth)acrylates include trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, trimethylolpropane alkylene oxide-modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, dipentaerythritol tri(meth)acrylate, trimethylolpropane tri((meth)acryloyloxypropyl) ether, isocyanuric acid alkylene oxide-modified tri(meth)acrylate, propionic acid dipentaerythritol tri(meth)acrylate, tri((meth)acryloyloxyethyl) isocyanurate, hydroxypival aldehyde-modified dimethylolpropane tri(meth)acrylate, sorbitol tri(meth)acrylate, propoxylated trimethylolpropane tri(meth)acrylate, and ethoxylated gly
  • tetrafunctional (meth)acrylates include pentaerythritol tetra(meth)acrylate, sorbitol tetra(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, propionic acid dipentaerythritol tetra(meth)acrylate, and ethoxylated pentaerythritol tetra(meth)acrylate.
  • pentafunctional (meth)acrylates examples include sorbitol penta(meth)acrylate and dipentaerythritol penta(meth)acrylate.
  • hexafunctional (meth)acrylates examples include dipentaerythritol hexa(meth)acrylate, sorbitol hexa(meth)acrylate, phosphazene alkylene oxide-modified hexa(meth)acrylate, and caprolactone-modified dipentaerythritol hexa(meth)acrylate.
  • (meth)acrylamides that can be used as the radical polymerizable monomer include (meth)acrylamide, N-methyl (meth)acrylamide, N-ethyl (meth)acrylamide, N-propyl (meth)acrylamide, N-n-butyl (meth)acrylamide, N-t-butyl (meth)acrylamide, N-butoxymethyl (meth)acrylamide, N-isopropyl (meth)acrylamide, N-methylol (meth)acrylamide, N,N-dimethyl (meth)acrylamide, N,N-diethyl (meth)acrylamide, and (meth)acryloyl morpholine.
  • radical polymerizable monomer in the present invention examples include vinyl esters [vinyl acetate, vinyl propionate, vinyl versate etc.], allyl esters [allyl acetate etc.], halogen-containing monomers [vinylidene chloride, vinyl chloride etc.], vinyl ethers [methyl vinyl ether, butyl vinyl ether, hexyl vinyl ether, methoxy vinyl ether, 2-ethyl hexyl vinyl ether, methoxyethyl vinyl ether, cyclohexyl vinyl ether, chloroethyl vinyl ether, triethyleneglycol divinyl ether etc.] and vinyl cyanides [(meth)acrylonitrile etc.], and olefins [ethylene, propylene etc.].
  • the radical polymerizable monomer in the present invention is preferably (meth)acrylates or (meth)acrylamides from the viewpoint of the curing rate, and more preferably a tetrafunctional or higher-functional (meth)acrylate from the viewpoint of the curing rate. From the viewpoint of the viscosity of the ink composition, it is preferable to use a combination of a multifunctional (meth)acrylate such as described above and a monofunctional or bifunctional (meth)acrylate or (meth)acrylamide.
  • Appropriate amount of the other polymerizable compound (a) in the ink composition is 50% by mass to 95% by mass, based on the total solid content of the composition; preferably, the content of the other polymerizable compound (a) in the ink composition is 60% by mass to 92% by mass, still preferably 70% by mass to 90% by mass, based on the total solid content of the composition
  • the ink composition of the present invention contains a pigment as an essential component. Owing to the function of the polymer, fine pigment particles with a small particle diameter are dispersed uniformly and stably in the ink composition, which allows the formation of sharp images excellent in coloring property.
  • the pigment is not particularly limited and may be appropriately selected from a wide variety of known pigments and dyes according to the purpose. Because the pigment is contained as a colorant, the images obtained by using the ink composition of the present invention are excellent in weather resistance.
  • the pigment contained in the ink composition of the present invention is not particularly limited.
  • Organic pigments and inorganic pigments that are usually available on the market and also, pigments obtained by dyeing resin particles with dyes may be used.
  • commercially available pigment dispersants and surface treated pigments for example, those obtained by dispersing pigments in an insoluble resin as a dispersion medium or those obtained by grafting a resin on the surface of a pigment may be used insofar as they do not impair the effect of the present invention.
  • pigments examples include the pigments described, for example, in Seijiro Itoh, "Dictionary of Pigments” (2000), W. Herbst and K. Hunger, “Industrial Organic Pigments ", and JP-A Nos. 2002-12607 , 2002-188025 , 2003-26978 , and 2003-342503 .
  • Examples of the organic and inorganic pigments contained in the ink composition of the present invention include the following.
  • Examples of pigments of yellow color include: monoazo pigments such as C.I. Pigment Yellow 1 (Fast Yellow G, etc.) and C.I. Pigment Yellow 74; disazo pigments such as C.I. Pigment Yellow 12 (Disazo Yellow, etc.), C.I. Pigment Yellow 17, C.I. Pigment Yellow 97, C.I. Pigment Yellow 3, C.I. Pigment Yellow 16, C.I. Pigment Yellow 83, ⁇ C.I. Pigment Yellow 155, and C.I. Pigment Yellow 219; non-benzidine azo pigments such as C.I. Pigment Yellow 180; azolake pigments such as C.I.
  • Pigment Yellow 100 (tartrazine yellow lake, etc.); condensation azo pigments such as C.I. Pigment Yellow 95 (Condensation Azo Yellow, etc.), C.I. Pigment Yellow 93, C.I. Pigment Yellow 94, C.I. Pigment Yellow 128, and C.I. Pigment Yellow 166; acidic-dye lake pigments such as C.I. Pigment Yellow 115 (quinoline yellow lake, etc.); basic-dye lake pigments such as C.I. Pigment Yellow 18 (thioflavin lake, etc.); anthraquinone pigments such as C.I. Pigment Yellow 24 (fravantrone yellow, etc.); quinophtharone pigments such as C.I.
  • Pigment Yellow 110 (quinophtharone yellow, etc.); isoindoline pigments such as C.I. Pigment Yellow 139 (isoindoline yellow, etc.); pyrazolone pigments such as C.I. Pigment Yellow 60 (pyrazolone yellow, etc.); acetolone pigments such as C.I. Pigment Yellow 120, C.I. Pigment Yellow 154, C.I. Pigment Yellow 167, C.I. Pigment Yellow 151, C.I. Pigment Yellow 175, C.I. Pigment Yellow 180, C.I. Pigment Yellow 181, and C.I. Pigment Yellow 194; metal-complex-salt pigments such as C.I. Pigment Yellow 150; nitroso pigments such as C.I. Pigment Yellow 153 (nickel nitroso yellow, etc.); and metal-complex-salt azomethine pigments such as C.I. Pigment Yellow 117 (copper azomethine yellow, etc.).
  • pigments of red or magenta color examples include: monoazo pigments such as C.I. Pigment Red 3 (toluidine red, etc.); B-naphthol pigments such as C.I. Pigment Red 1, C.I. Pigment Red 4, and C.I. Pigment Red 6; disazo pigments such as C.I. Pigment Red 38 (Pyrazolone Red B, etc.); azolake pigments such as C.I. Pigment Red 53:1 (Lake Red C, etc.), C.I. Pigment Red 57:1 (Brilliant Carmine 6B, etc.), C.I. Pigment Red 52:1, and C.I.
  • Pigment Red 48 (B-oxynaphthoic acid Lake, etc.); condensation azo pigments such as C.I. Pigment Red 144, C.I. Pigment Red 166, C.I. Pigment Red 220, C.I. Pigment Red 214, C.I. Pigment Red 221, and C.I. Pigment Red 242 (Condensation Azo Red, etc.); acidic dye lake pigments such as C.I. Pigment Red 174 (Phloxine B Lake, etc.) and C.I. Pigment Red 172 (Erythrosine Lake, etc.); basic dye lake pigments such as C.I.
  • Pigment Red 81 (Rhodamine 6G' Lake, etc.); anthraquinone pigments such as C.I. Pigment Red 177 (dianthraquinolyl red, etc.); thioindigo pigments such as C.I. Pigment Red 88 (Thioindigo Bordeaux, etc.); perynone pigments such as C.I. Pigment Red 194 (perynone red, etc.); perylene pigments such as C.I. Pigment Red 149, C.I. Pigment Red 179, C.I. Pigment Red 178, C.I. Pigment Red 190, C.I. Pigment Red 224, and C.I. Pigment Red 123; quinacridone pigments such as C.I.
  • Pigment Violet 19 (unsubstituted quinacridone), C.I. Pigment Red 122, C.I. Pigment Red 262, C.I. Pigment Red 207, and C.I. Pigment Red 209; isoindolinone pigments such as C.I. Pigment Red 180 (Isoindolinone Red 2BLT, etc.); alizarin lake pigments such as C.I. Pigment Red 83 (madder lake, etc.); naphtholone pigments such as C.I. Pigment Red 171, C.I. Pigment Red 175, C.I. Pigment Red 176, C.I. Pigment Red 185, and C.I. Pigment Red 208; naphthol AS lake pigments such as C.I.
  • Pigment Red 247 naphthol AS pigments such as C.I. Pigment Red 2, C.I. Pigment Red 5, C.I. Pigment Red 21, C.I. Pigment Red 170, C.I. Pigment Red 187, C.I. Pigment Red 256, C.I. Pigment Red 268, and C.I. Pigment Red 269; and diketopyrrolopyrrole pigments such as C.I. Pigment Red 254, C.I. Pigment Red 255, C.I. Pigment Red 264, and C.I. Pigment Red 272.
  • blue or cyan pigments examples include disazo pigments such as C.I. Pigment Blue 25 (dianisidine blue, etc.); phthalocyanine pigments such as C.I. pigment blue 15, C.I. pigment blue 15:1, C.I. pigment blue 15:2, C.I. pigment blue 15:3, C.I. pigment blue 15:4, C.I. pigment blue 15:6, and C.I. pigment blue 16 (phthalocyanine blue, etc.); acidic dye lake pigments such as C.I. pigment blue 24 (peacock blue lake, etc.); basic dye lake pigments such as C.I. Pigment Blue 1 (Victoria Pure Blue BO Lake, etc.); anthraquinone pigments such as C.I. pigment blue 60 (indanthron blue, etc.); and alkali blue pigments such as C.I. Pigment Blue 18 (alkali blue V-5:1).
  • disazo pigments such as C.I. Pigment Blue 25 (dianisidine blue, etc.
  • phthalocyanine pigments such as C.
  • green pigments examples include phthalocyanine pigments such as C.I. Pigment Green 7 (phthalocyanine green) and C.I. Pigment Green 36 (phthalocyanine green); and azo metal complex pigments such as C.I. Pigment Green 8 and C.I. Pigment Green 10.
  • orange pigments examples include isoindoline pigments such as C.I. Pigment Orange 66 (isoindoline orange); anthraquinone pigments such as C.I. Pigment Orange 51 (dichloropyranthron orange); B-naphthol pigments such as C.I. Pigment Orange 2, C.I. Pigment Orange 3, and C.I. Pigment Orange 5; naphthol AS pigments such as C.I. Pigment Orange 4, C.I. Pigment Orange 22, C.I. Pigment Orange 24, C.I. Pigment Orange 38, and C.I. Pigment Orange 74; isoindolinone pigments such as C.I. Pigment Orange 61; perynone pigments such as C.I.
  • Pigment Orange 43 disazo pigments such as C.I. Pigment Orange 15 and C.I. Pigment Orange 16; quinacridone pigments such as C.I. Pigment Orange 48 and C.I. Pigment Orange 49; acetolone pigments such as C.I. Pigment Orange 36, C.I. Pigment Orange 62, C.I. Pigment Orange 60, C.I. Pigment Orange 64, and C.I. Pigment Orange 72; and pyrazolone pigments such as C.I. Pigment Orange 13 and C.I. Pigment Orange 34.
  • disazo pigments such as C.I. Pigment Orange 15 and C.I. Pigment Orange 16
  • quinacridone pigments such as C.I. Pigment Orange 48 and C.I. Pigment Orange 49
  • acetolone pigments such as C.I. Pigment Orange 36, C.I. Pigment Orange 62, C.I. Pigment Orange 60, C.I. Pigment Orange 64, and C.I. Pigment Orange 72
  • brown pigments examples include naphtholone pigments such as C.I. Pigment Brown 25 and C.I. Pigment Brown 32.
  • violet pigments examples include naphtholone pigments such as C.I. Pigment Violet 32; perylene pigments such as C.I. Pigment Violet 29; naphthol AS pigments such as C.I. Pigment Violet 13, C.I. Pigment Violet 17, and C.I. Pigment Violet 50; and dioxazine pigments such as C.I. Pigment Violet 23 and C.I. Pigment Violet 37.
  • black pigments examples include indazine pigments such as carbon black, titanium black, and C.I. Pigment Black 1 (aniline black); and perylene pigments such as C.I. Pigment Black 31 and C.I. Pigment Black 32.
  • white pigments include basic lead carbonate (2PbCO 3 Pb(OH) 2 , so-called silver white), zinc oxide (ZnO, so-called zinc white), titanium oxide (TiO 2 , so-called titanium white), and strontium titanate (SrTiO 3 , so-called titanium strontium white).
  • the inorganic particles to be used for white pigment may be particles of a simple substance, or may be an oxide of, for example, silicon, aluminum, zirconium, or titanium, or composite particles with an organometallic compound or an organic compound.
  • titanium oxide Since titanium oxide has a lower specific gravity and a higher refractive index than other white pigments and is more stable chemically or physically, titanium oxide has a greater masking and coloring potential as a pigment, and is further excellent in resistance to acid or alkali and other environmental factors. Thus, the use of titanium oxide as a white pigment is preferable. Of course, other white pigment (including white pigments other than those described above) may be used as necessary.
  • dispersing machines such as a ball mill, a sand mill, an attriter, a roll mill, a jet mill, a homogenizer, a paint shaker, a kneader, an agitator, a Henschel mixer, a colloid mill, an ultrasonic wave homogenizer, a pearl mill, and a wet jet mill, can be used.
  • the pigment is dispersed, it is preferable to add the polymer of the present invention.
  • a synergist suitable for the pigment may be used as a dispersing aid as necessary.
  • the dispersing aid is preferably added in an amount of 1 part by mass to 50 parts by mass based on 100 parts by mass of the pigment.
  • a solvent may be added as the dispersion medium for various components such as pigment, or the other polymerizable compound (a), which is a low-molecular-mass component, may be used as a solvent-free dispersion medium.
  • the ink composition according to the present invention is preferably free of solvent because the composition is preferably a radiation-curable ink that is cured after applied onto a recording medium. If the solvent remains in the cured ink image, solvent resistance may be deteriorated and a problem of VOC (Volatile Organic Compound) may occur.
  • the dispersion medium is preferably a other polymerizable compound (a), particularly preferably a polymerizable compound having the lowest viscosity, in view of the improvement in the dispersibility and handling property of the ink composition.
  • the average particle diameter of the pigment to be used is preferably in the range of about 0.01 ⁇ m to 0.4 ⁇ m, more preferably in the range of 0.02 ⁇ m to 0.2 ⁇ m.
  • the maximum particle diameter may be 3 ⁇ m, preferably 1 ⁇ m; such a maximum particle diameter can be achieved by appropriate selections of the pigment (b), the dispersant, the dispersing medium, the dispersion conditions, and the filtration conditions.
  • the particle diameter of the pigment in the ink composition can be measured by a known measurement method. Specifically, the particle diameter can be measured by a centrifugal-sedimentation light-transmission method, an X-ray transmission method, a laser diffraction/scattering method, or a dynamic light scattering method.
  • the amount of the pigment in the ink composition is preferably 1% by mass to 20% by mass, more preferably 2% by mass to 10% by mass, in terms of solid content.
  • the amount of the pigment in the ink composition is preferably 1% by mass to 30% by mass, more preferably 2% by mass to 25% by mass, in terms of solid content.
  • the ink composition of the present invention preferably contains a radical polymerization initiator or a cation polymerization initiator and more preferably contains a photopolymerization initiator.
  • the photopolymerization initiator in the present invention is a compound that is changed chemically through the action of light or an interaction with a sensitizing dye put in an electron excited state to produce at least one of a radical, an acid and a base.
  • the photopolymerization initiator may be selected appropriately from initiators having sensitivity to the activated ray for irradiation, such as UV ray at 400 nm to 200 nm, far UV ray, g-line, h-line, i-line, KrF excimer laser light, ArF excimer laser light, electron ray, X-ray, molecular beam, or ion beam.
  • initiators having sensitivity to the activated ray for irradiation such as UV ray at 400 nm to 200 nm, far UV ray, g-line, h-line, i-line, KrF excimer laser light, ArF excimer laser light, electron ray, X-ray, molecular beam, or ion beam.
  • any of common photopolymerization initiators known in the art may be used. Examples thereof are described, for example, in Bruce M. Monroe et al., Chemical Revue, 93,435 (1993 ); R. S. Davidson, Journal of Photochemistry and biology A: Chemistry, 73, 81 (1993 ); J. P. Faussier, "Photoinitiated Polymerization-Theory and Applications”: Rapra Review vol. 9, Report, Rapra Technology (1998 ); and M. Tsunooka et al., Prog. Polym. Sci., 21,1 (1996 ).
  • photopolymerization initiators include (i) aromatic ketones, (ii) aromatic onium salt compounds, (iii) organic peroxides, (iv) hexaarylbiimidazole compounds, (v) ketoxime ester compounds, (vi) borate compounds, (vii) azinium compounds, (viii) metallocene compounds, (ix) active ester compounds, and (x) compounds containing a carbon-halogen bond.
  • acylphosphine oxide may also be used as the photopolymerization initiator.
  • aromatic onium salt compounds (ii) include aromatic onium salts of the elements in Groups V, VI and VII in the periodic table, specifically, aromatic onium salts of N, P, As, Sb, Bi, O, S, Se, Te, and I.
  • aromatic onium salts described in EP Patent No. 104143 , U.S. Patent No. 4837124 , and JP-A Nos. 2-150848 and 2-96514 ; the sulfonium salts described in EP Patent Nos. 370693 , 233567 , 297443 , 297442 , 279210 , and 422570 and U.S. Patent Nos.
  • diazonium salts e.g., benzene diazonium salts which may have one or more substituted groups
  • diazonium salt resins e.g., formaldehyde resins of diazodiphenylamine
  • N-alkoxypyridinium salts e.g., those described in U.S. Patent No. 4,743,528 , JP-A Nos. 63-138345 , 63-142345 , and 63-142346 , and JP-B No.
  • the aromatic onium salt compound (ii) generates a radical or an acid as an active species.
  • organic peroxides (iii) include almost all organic compounds having one or more oxygen-oxygen bonds in the molecule; and preferable examples thereof include peroxide esters such as 3,3',4,4'-tetra-(t-butylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra-(t-amylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra-(t-hexylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra-(t-octylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra-(cumylperoxycarbonyl)benzophenone, 3,3',4,4'-tetra-(p-isopropyl cumylperoxycarbonyl)benzophenone, and di-t-butyl diperoxyisophthalate.
  • peroxide esters such as 3,3',4,4'
  • hexaarylbiimidazole compounds (iv) include the Rofin dimers described in JP-B Nos. 45-37377 and 44-86516 , such as 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-bromophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-,p-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetra(m-methoxyphenyl)biimidazole, 2,2'-bis(o-,o'-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(o
  • ketoxime ester compounds (v) examples include 3-benzoyloxyiminobutan-2-one, 3-acetoxyiminobutan-2-one, 3-propionyloxyiminobutan-2-one, 2-acetoxyiminopentane-3-one, 2-acetoxyimino-1-phenylpropan-1-one, 2-benzoyloxyimino-1-phenylpropan-1-one, 3-p-toluenesulfonyloxyiminobutan-2-one, and 2-ethoxycarbonyloxyimino-1-phenylpropan-1-one.
  • borate compounds (vi) examples include the compounds described in U.S. Patent Nos. 3,567,453 and 4,343,891 , and EP Patent No. 109,772 and 109,773 .
  • Examples of the azinium compounds (vii) include the compounds containing an N-O bond described in JP-A Nos. 63-138345 , 63-142345 , 63-142346 , and 63-143537 , and JP-B No. 46-42363 .
  • Examples of the metallocene compounds (viii) include the titanocene compounds described in JP-A Nos. 59-152396 , 61-151197 , 63-41484 , 2-249 , and 2-4705 and the iron-allene complexes described in JP-A Nos. 1-304453 and 1-152109 .
  • titanocene compounds examples include di-cyclopentadienyl-Ti-dichloride, di-cyclopentadienyl-Ti-bisphenyl, di-cyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,3,5,6-tetrafluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4,6-trifluorophen-1-yl, di-cyclopentadienyl-Ti-2,6-difluorophen-1-yl, di-cyclopentadienyl-Ti-bis-2,4-difluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,3,4,5,6-pentafluorophen-1-yl, di-methylcyclopentadienyl-Ti-bis-2,
  • Examples of the active ester compounds (ix) include nitrobenzyl ester compounds described in EP Patent Nos. 0290750 , 046083 , 156153 , 271851 , and 0388343 , U.S. Patent Nos. 3,901,710 and 4,181,531 , and JP-A Nos. 60-198538 and 53-133022 ; iminosulfonate compounds described in EP Patent Nos. 0199672 , 84515 , 199672 , 044115 , and 0101122 , U.S. Patent Nos. 4,618,564 , 4,371,605 , and 4,431,774 , and JP-A Nos. 64-18143 , 2-245756 and 4-365048 ; and compounds described in JP-B Nos. 62-6223 and 63-14340 , and JP-A No. 59-174831 .
  • Examples of the compounds (x) containing a carbon-halogen bond include compounds described in Wakabayashi et al., Bull. Chem. Soc. Japan, 42, 2924 (1969 ), compounds described in British Patent No. 1388492 , compounds described in JP-A No. 53-133428 , and compounds described in German Patent No. 3337024 .
  • Examples of the compounds containing a carbon-halogen bond include compounds described in F. C. Schaefer et al., J. Org. Chem. 29,1527 (1964 ), compounds described in JP-A No. 62-58241 , compounds described in JP-A No. 5-281728 , compounds described in German Patent No. 2641100 , compounds described in German Patent No. 3333450 , compounds described in German Patent No. 3021590 , and compounds described in German Patent No. 3021599 .
  • the content of the photopolymerization initiator in the ink composition is preferably 0.1% by mass to 20% by mass, more preferably 0.5% by mass to 10% by mass, most preferably 1% by mass to 7% by mass, based on the total solid content in the ink composition.
  • a sensitizing dye may be added for the purpose of improving the sensitivity of the photopolymerization initiator.
  • the sensitizing dye those are preferable that belong to the following compound classes and have absorption wavelengths in the range of 350 nm to 450 nm.
  • the sensitizing dye examples include multinuclear aromatics (e.g., pyrene, perylene, triphenylene, and anthracene), xanthenes (e.g., fluorescein, eosin, erythrosine, rhodamine B, and Rose Bengal), cyanines (e.g., thiacarbocyanine and oxacarbocyanine), merocyanines (e.g., merocyanine and carbomerocyanine), thiazines (e.g., thionine, methylene blue, and toluidine blue), acridines (e.g., acridine orange, chloroflavin, and acryflavin), anthraquinones (e.g., anthraquinone), squaliums (e.g., squalium), and coumarins (e.g., 7-diethylamino-4-methyl coumarin
  • a 1 represents a sulfur atom or -NR 50 -
  • R 50 represents an alkyl group or an aryl group
  • L 2 represents a nonmetallic atomic group which, together with A 1 and the carbon atom adjacent thereto, forms a basic nucleus of a dye
  • R 51 and R 52 each independently represent a hydrogen atom or a monovalent nonmetallic atomic group
  • R 51 and R 52 may be bound to each other to form an acidic nucleus of a dye
  • W represents an oxygen atom or a sulfur atom.
  • Ar 1 and Ar 2 each independently represent an aryl group, and are bound to each other via a linkage -L 3 - which represents -O- or -S-.
  • W has the same definition as in formula (IX).
  • a 2 represents a sulfur atom or NR 59
  • L 4 represents a nonmetallic atomic group which, together with A 2 and the carbon atom adjacent thereto, forms a basic nucleus of a dye
  • R 53 , R 54 , R 55 , R 56 , R 57 and R 58 each independently represent a monovalent nonmetallic atomic group
  • R 59 represents an alkyl group or an aryl group.
  • a 3 and A 4 each independently represent -S- or -NR 62 - or -NR 63 -.
  • R 62 and R 63 each independently represent a substituted or unsubstituted alkyl group or a substituted or unsubstituted aryl group.
  • L 5 represents a nonmetallic atomic group which, together with A 3 and the carbon atom adjacent thereto, forms a basic nucleus of a dye.
  • L 6 represents a nonmetallic atomic group which, together with A 4 and the carbon atom adjacent thereto, forms a basic nucleus of a dye.
  • R 60 and R 61 each independently represent a hydrogen atom or a monovalent nonmetallic atomic group, or R 60 and R 61 are bound to each other to form an aliphatic or aromatic ring.
  • R 66 represents an optionally substituted aromatic cycle or heterocycle
  • a 5 represents an oxygen atom, a sulfur atom, or -NR 67 -.
  • R 64 , R 65 , and R 67 each independently represent a hydrogen atom or a monovalent nonmetallic atomic group.
  • R 67 and R 64 may be bonded to each other to form an aliphatic or aromatic ring.
  • R 65 and R 67 may be bonded to each other to form an aliphatic or aromatic ring.
  • a known compound that has a function of further improving the sensitivity or suppressing the inhibition of polymerization by oxygen may be added as a cosensitizer.
  • cosensitizer examples include the amines described, for example, in M. R. Sander et al., "Journal of Polymer Society" 10, p. 3173, (1972 ), JP-B No. 44-20189 , JP-A Nos. 51-82102 , 52-134692 , 59-138205 , 60-84305 , 62-18537 , and 64-33104 and Research Disclosure 33825; and specific examples thereof include triethanolamine, ethyl p-dimethylaminobenzoate, p-formyldimethylaniline, and p-methylthiodimethylaniline.
  • cosensitizer examples include thiols and sulfides, for example, the thiol compounds described in JP-A No. 53-702 , JP-B No. 55-500806 , and JP-A No. 5-142772 , and the disulfide compounds described in JP-A No. 56-75643 ; and specific examples thereof include 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, 2-mercaptobenzimidazole, 2-mercapto-4(3H)-quinazoline, and b-mercaptonaphthalene.
  • cosensitizer examples include amino acid compounds (e.g., N-phenylglycine), the organic metal compounds described in JP-B No. 48-42965 (e.g., tributyltin acetate), the hydrogen donors described in JP-B No. 55-34414 , the sulfur compounds described in JP-A No. 6-308727 (e.g., trithiane), the phosphorus compounds described in JP-A No. 6-250387 (e.g., diethyl phosphite), and the Si-H and Ge-H compounds described in JP-A No. 6-191605 .
  • amino acid compounds e.g., N-phenylglycine
  • the organic metal compounds described in JP-B No. 48-42965 e.g., tributyltin acetate
  • the hydrogen donors described in JP-B No. 55-34414 the hydrogen donors described in JP-B No. 55-34414
  • the ink composition according to the present invention may further contain various additives according to the purpose.
  • an ultraviolet absorbent may be added to the ink composition according to the present invention, for the improvement in the weather resistance of the obtained image and prevention of the discoloration of the image.
  • an antioxidant may be added to improve the stability of the ink composition.
  • Other usable additives include: an organic or metal-complex-based anti-fading agent; a conductive salt for the control of the ejection properties, such as potassium thiocyanate, lithium nitrate, ammonium thiocyanate, or dimethylamine hydrochloride salt; and a trace amount of an organic solvent for the improvement of the adhesion to the recording medium.
  • an organic or metal-complex-based anti-fading agent such as potassium thiocyanate, lithium nitrate, ammonium thiocyanate, or dimethylamine hydrochloride salt
  • a trace amount of an organic solvent for the improvement of the adhesion to the recording medium.
  • the ink composition according to the present invention may further contain a polymer compound selected from various polymer compounds for the purpose of the adjustment of the film physical properties.
  • polymer compounds include acrylic polymers, polyvinylbutyral resins, polyurethane resins, polyamide resins, polyester resins, epoxy resins, phenol resins, polycarbonate resins, polyvinylbutyral resins, polyvinylformal resins, shellac, vinyl resins, acrylic resins, rubber resin, waxes, and other natural resins. Two or more polymer compounds may be used simultaneously.
  • One or more substances selected from nonionic surfactants, cationic surfactants, and organic fluorocompounds may be added to the ink composition of the present invention in order to control the liquid properties.
  • the ink composition of the present invention may contain other additives as necessary, for example, leveling additives, matting agents, waxes for controlling the film properties, and tackifiers, which do not inhibit polymerization, for improving the adhesion to recording media such as polyolefin and PET.
  • leveling additives for example, leveling additives, matting agents, waxes for controlling the film properties, and tackifiers, which do not inhibit polymerization, for improving the adhesion to recording media such as polyolefin and PET.
  • the ink composition of the present invention has a viscosity of preferably 30 mPa ⁇ s or less and more preferably 20 mPa ⁇ s or less at the temperature of injection taking injection ability into account. It is preferable to control and determine the ratio of the composition properly such that the viscosity of the ink composition falls in the above range. It is to be noted that the viscosity of the ink at 25°C (room temperature) is 200 mPa ⁇ s or less and preferably 100 mPa ⁇ s.
  • the surface tension of the ink composition according to the present invention is preferably 20 mN/m to 30 mN/m and more preferably 23 mN/m to 28 mN/m.
  • the surface tension is preferably 20 mN/m or more in view of the prevention of bleeding and penetration, and 30 mN/m or less in view of the wettability.
  • the ink composition of the present invention prepared in this manner is suitably used as an inkjet recording ink.
  • the recording can be conducted by applying the ink composition on a recording medium by printing using an inkjet printer, and then irradiating the applied ink composition with a radiation ray to cure the composition.
  • the image portion has been cured by irradiation with radiation rays such as ultraviolet rays and the printed articles are therefore superior in the strength of the image portion. Therefore, the ink composition of the present invention may be used in various applications such as the formation of the ink receptor layer (image portion) of a planographic printing plate, besides image formation using ink.
  • the inkjet recording method it is preferable to eject the ink composition after the viscosity of ink composition is lowered to 30 mPa ⁇ s or less by heating to 40°C to 80°C, and in this manner, it is possible to realize highly stable ejection.
  • Radiation-curable ink compositions are usually more viscous than aqueous inks.
  • fluctuation in the viscosity of radiation-curable ink compositions caused by the fluctuation in temperature during printing is larger.
  • the fluctuation in the viscosity of ink composition exerts significant influences on the droplet size and the droplet ejection speed, causing deterioration in image quality, and thus, it is necessary to keep the temperature of the ink composition as constant as possible during printing.
  • the inkjet recording apparatus may have an ink-temperature stabilizing device.
  • the ink-temperature stabilizing device maintains a constant temperature of the ink composition in all the piping systems and members from the ink tank (from the intermediate tank if such an intermediate tank is present) to the ejection face on the nozzles.
  • the temperature can be controlled by any method without limitation. For example, it is preferable to control heating conditions according to the flow rate of the ink composition and the environmental temperature based on the information supplied from plural temperature sensors provided to the respective pipes.
  • the heat unit to be heated is preferably insulated thermally such that the unit is not affected by the environmental temperature.
  • the heat unit is thermally insulated from the other portions, and the total heat capacity of the heating unit is small, whereby the printer starting-up time required for heating is shortened and the heat energy loss is reduced.
  • An active radiation-curable ink composition can be obtained by adding the photopolymerization initiator as the polymerization initiator (c) to the ink composition of the present invention.
  • JP-A No. 60-132767 A basic method of the irradiation is disclosed in JP-A No. 60-132767 . Specifically, light sources are disposed at both sides of a head unit, and the head unit and the light sources are scanned in the shuttle mode. The ink composition is irradiated with the active radiation ray after a predetermined period from the deposition of the ink composition on the recording medium. The ink composition is cured using another light source that is not driven.
  • WO 99/54415 discloses an irradiation method comprising using an optical fiber and an irradiation method comprising irradiating the recording area with UV rays by directing a collimated rays to a mirror surface on the sidewall of head unit. These irradiation methods may be used in the present invention.
  • the ink composition it is desirable to heat the ink composition to a predetermined temperature and adjust the period between the deposition of the ink composition on the recording medium and the irradiation with radiation rays to 0.01 second to 0.5 second, preferably 0.01 second to 0.3 second, and more preferably 0.01 second to 0.15 second. It becomes possible to prevent bleeding of the deposited ink composition before curing, by shortening the period between the deposition of the ink composition on the recording medium and the irradiation with radiation rays to such an extremely short period. Further, even when the recording medium is porous, the ink composition is irradiated before penetrating deep into the recording medium.
  • the inkjet recording method and the ink composition of the present invention provides significant synergy effects.
  • the viscosity of the ink composition at 25°C is 200 mPa ⁇ s or less, significant effects can be obtained.
  • By employing such an inkjet recording method it is possible to maintain the dot diameter of the deposited ink composition constant and obtain an image with improved quality, on any of various recording media different in surface wettability. In order to obtain a color image, it is preferable to form images in the order from a color lower in lightness.
  • the inkjet recording apparatus used in the present invention is not particularly limited, and a commercial inkjet recording apparatus can be used.
  • the recording on recording media printed articles
  • the recording on recording media can be conducted by a commercial inkjet recording apparatus.
  • the ink composition of the present invention is repeatedly heated and cooled, reduction in pigment dispersibility is avoided, excellent coloring property is achieved over a long period, and the deterioration of the ejection property caused by the aggregation of the pigment is also avoided owing to the function of the specific polymer that contains a copolymer unit derived from the monomers represented by the formula (1) to (3) even when the ink composition is stored under such temperature conditions.
  • the recording medium to which the ink composition according to the present invention is applicable is not particularly limited, and examples thereof include ordinary papers such as non-coated paper, coated paper, and corrugated paper, various non-absorptive resin materials for use in so-called soft packaging, and resin films thereof in the film shape.
  • various plastic films include PET film, OPS film, OPP film, ONy film, PVC film, PE film, and TAC film.
  • other plastics usable as the material of the recording medium include polycarbonate, acrylic resins, ABS, polyacetal, PVA, and rubbers.
  • metals and glasses are also usable as the recording media. Recording media having a large area may also be used.
  • the ink composition of the present invention is used to print on a recording medium by an inkjet printer and then, preferably, the ink composition applied by printing is irradiated with an active radiation ray and cured, whereby the printed articles of the present invention can be obtained.
  • the printed article of the present invention has a high quality image superior in coloring property and sharpness and is also superior in the weather resistance of the image because the ink used for image formation contains fine pigment particles uniformly and stably in a dispersed state.
  • the ink composition of the invention is therefore applied in a wide range of fields.
  • graft copolymer 1 A copolymer of the monomer represented by M-1, and polymethylmethacrylate having a methacryloyl group at its terminal).
  • V-65 2,2-azobis(2,4-dimethylvaleronitrile)
  • V-65 2,2-azobis(2,4-dimethylvaleronitrile)
  • the resulting reaction solution was poured into 1,000 mL of hexane with stirring, and the precipitates produced were heated and dried to obtain a graft copolymer 2
  • the above listed graft copolymer 8 A copolymer of the monomer represented by M-1, 3-(N,N-dimethylamino)propyl acrylamide, and polymethylmethacrylate having a methacryloyl group at its terminal).
  • a graft copolymer 3 (the above listed graft copolymer 2: A copolymer of the monomer represented by M-1, and polyethylene glycol mono(meth)acrylate) was obtained in the same way as in the synthetic example of graft copolymer 1 except that the "polymethyl methacrylate having a methacryloyl group at one terminal" of the synthetic example of graft copolymer 1 was changed to "methoxypolyethylene glycol methacrylate" (NK ESTER M-230G, manufactured by Shin-Nakamura Chemical Co., Ltd.).
  • a graft copolymer 4 (the above listed graft copolymer 4: A copolymer of the monomer represented by M-1, and polybutyl acrylate having a methacryloyl group at its terminal) was obtained in the same way as in the synthetic example of graft copolymer 1 except that the "polymethyl methacrylate having a methacryloyl group at one terminal" of the synthetic example of graft copolymer 1 was changed to "polybutyl acrylate having a methacryloyl group at one terminal" (AB-6, manufactured by Toagosei Co., Ltd.).
  • a graft copolymer 5 (the above listed graft copolymer 5: A copolymer of the monomer represented by M-3, and polymethylmethacrylate having a methacryloyl group at its terminal) was obtained in the same way as in the synthetic example of graft copolymer 1 except that M-1 of the synthetic example of graft copolymer 1 was changed to M-3.
  • a graft copolymer 6 (the above listed graft copolymer 16: A copolymer of the monomer represented by M-1, methacrylic acid, and polymethylmethacrylate having a methacryloyl group at its terminal) was obtained in the same way as in the synthetic example of graft copolymer 2 except that the "3-(N,N-dimethylaminopropyl acrylamide)" of the synthetic example of graft copolymer 2 was changed to "methacrylic acid".
  • Graft copolymer 1 (the graft copolymer 1 listed above: copolymer of the monomer, represented by M-1, and polymethylmethacrylate having a methacryloyl group at its terminal) was dissolved in other polymerizable compounds (a), (i) and (ii), and the mixture was placed together with a pigment (b) in a Motor Mill M50 (manufactured by Eiger Co., Ltd.) to disperse the mixture at a peripheral speed of 9 m/s for 6 hours by using zirconia beads 0.65 mm in diameter, thereby obtaining a reaction mixture of active energy ray-curable ink.
  • a the graft copolymer 1 listed above: copolymer of the monomer, represented by M-1, and polymethylmethacrylate having a methacryloyl group at its terminal
  • Active energy ray-curable type inkjet inks of Examples 2 to 6 were obtained in the same way as in Example 1 except that the graft copolymer 1 used in Example 1 was changed to the graft copolymers 2 to 6, respectively, prepared in the synthetic examples.
  • An active energy ray-curable type inkjet ink of Comparative Example 1 was obtained in the same way as in Example 1 except that a commercially available pigment dispersant "SOLSPERSE 24000GR" (manufactured by Lubrizol Japan Ltd.) was used instead of the graft copolymer 1 used in Example 1.
  • An active energy ray-curable type inkjet ink of Comparative Example 2 was obtained in the same way as in Example 1 except that a commercially available pigment dispersant "SOLSPERSE 32000" (manufactured by Lubrizol Japan Ltd.) was used instead of the graft copolymer 1 used in Example 1.
  • Inkjet ink compositions of Example 7 and Comparative Examples 3 and 4 were obtained in the same way as in Example 2 and Comparative Examples 1 and 2, respectively, except that the quinacridone base pigment PV-19 (b) was changed to PY-128.
  • Example 8 and Comparative Examples 5 and 6 were obtained in the same way as in Example 2 and Comparative Examples 1 and 2, respectively, except that the other polymerizable compound (a) and polymerization initiator (c) were changed to the following compounds.
  • Example 9 and Comparative Examples 7 and 8 were obtained in the same way as in Example 8 and Comparative Examples 5 and 6, respectively, except that the quinacridone base pigment PV-19 was changed to a phthalocyanine-based pigment PB15:3.
  • the polymer of the present invention shown below (graft copolymer 2) was dissolved in the following polymerizable compounds (a), and the mixture was placed together with the following pigment (b) in a Motor Mill M50 (manufactured by Eiger Co., Ltd.) to disperse the mixture at a peripheral speed of 5 m/ s for 5 hours by using zirconia beads 0.65 mm in diameter, thereby obtaining a reaction mixture of active energy ray-curable ink. Then, a polymerization initiator (c) was added to the reaction mixture and mixed mildly, followed by filtration under pressure using a membrane filter to obtain an inkjet ink of Example 10.
  • An inkjet ink of Comparative Example 9 was obtained in the same way as in Example 10 except that the polymer of the present invention (graft copolymer 2) used in Example 10 was changed to a commercially available pigment dispersant "SOLSPERSE 24000GR" (manufactured by Lubrizol Japan Ltd.).
  • Example 11 and Comparative Example 10 were obtained in the same way as in Example 10 and Comparative Example 9, respectively, except that the pigment (b) used in Example 10 and Comparative Example 9 was changed to acetolone pigment (PY-120, Novoperm Yellow H2G, manufactured by Clariant(Japan)K.K.).
  • acetolone pigment PY-120, Novoperm Yellow H2G, manufactured by Clariant(Japan)K.K.
  • Example 12 An inkjet ink of Example 12 was obtained in the same way as in Example 10 except that the polymerizable compound (a), pigment (b), polymerization initiator (c) used in Example 10 were changed to following compounds.
  • An inkjet ink of Comparative Example 11 was obtained in the same way as in Example 12 except that the polymer of the present invention (graft copolymer 2) used in Example 12 was changed to a commercially available pigment dispersant "SOLSPERSE 24000GR" (manufactured by Lubrizol Japan Ltd.).
  • the viscosity of each inkjet ink at 40°C was measured with an E-type viscometer.
  • the volumetric average particle diameter D50 of each inkjet ink was measured using a light-scattering diffraction type particle size distribution measuring device (LA910, manufactured by Horiba, Ltd.) to carry out evaluation.
  • LA910 light-scattering diffraction type particle size distribution measuring device
  • the obtained ink compositions were applied to art paper by printing using an inkjet printer (printing density: 300 dpi, dotting frequency: 4 kHz, number of nozzles: 64) and then exposed to light by using a Deep UV lamp (SP-7, manufactured by Ushio Inc.) under an energy condition of 100 mJ/cm 2 to obtain a print sample.
  • an inkjet printer printing density: 300 dpi, dotting frequency: 4 kHz, number of nozzles: 64
  • SP-7 Deep UV lamp
  • a cured coating film was touched with fingers to evaluate the presence of a sticky feel according to the following standard.
  • the ink composition of the present invention was cured with high sensitivity when irradiated with a radiation ray, and it could therefore form a non-sticky high quality image. Even in the case where it was stored for a long time, the dispersibility and dispersion stability of the pigment were both satisfactory without any increase in viscosity associated with a reduction in the dispersibility of the pigment.
  • the polymer of the present invention comprises, as a basic building block, a site interacting with a pigment, and a graft chain (macromonomer).
  • the site interacting with a pigment indicates the polymerizable compound of the present invention, and, according to necessity, also includes a basic monomer or acidic monomer (those which interact with acidic or basic site of the pigment surface).
  • the graft chain (macromonomer) has a higher affinity for a dispersion medium than for a pigment and functions as a steric repulsive site that prevents the particles from aggregating in the dispersion liquid. Thus, it is necessary to select a graft chain depending on the dispersion medium.
  • the ink composition of the present invention can be suitably used in usual printing to form a sharp image with excellent coloring property, thus giving a high-quality printed material.
  • the ink composition of the present invention can be suitably used also in the production of resists, color filters, and optical disks, and is useful also as an optical molding material.
  • the ink composition of the present invention can be suitably used also for the production of a printed material having a large area.

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  • Materials Engineering (AREA)
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Claims (10)

  1. Tintenzusammensetzung, umfassend:
    ein Polymer, das eine Copolymereinheit umfasst, die aus einem durch die Formel (1) dargestellten Monomer erhalten ist, wie nachstehend beschrieben,
    eine polymerisierbare Verbindung (a); und
    ein Pigment (b)
    Figure imgb0059
    worin in der Formel (1) R1 irgendeines von einem Wasserstoffatom, einer substituierten Alkylgruppe und
    einer unsubstitutierten Alkylgruppe darstellt; R2 eine Alkylengruppe darstellt; W irgendeines von -CO-, -C(=O)O-, -CONH-, -OC(=O)- und einer Phenylengruppe darstellt; X irgendeines von -CO-, -NHCO-, -OC(=0)-, -CH(OH)CH2- und -SO2- darstellt; R3 und R4 jeweils einen optional vorhandenen monovalenten Substituenten darstellen können; und m und n jeweils unabhängig 0 oder 1 darstellen.
  2. Tintenzusammensetzung gemäß Anspruch 1, worin das Monomer der Formel (1) durch die folgende Formel (2) dargestellt wird:
    Figure imgb0060
     worin in der Formel (2) R3 und R4 jeweils einen optional vorhandenen monovalenten Substituenten darstellen können.
  3. Tintenzusammensetzung gemäß Anspruch 1, worin das Polymer ferner eine Copolymereinheit umfasst, die aus einem durch die Formel (2) dargestellten Monomer erhalten ist, wie in Anspruch 2 definiert.
  4. Tintenzusammensetzung gemäß irgendeinem der Ansprüche 1 und 2, worin das Polymer ein Pfropf-Copolymer ist, das als eine Copolymereinheit ein polymerisierbares Oligomer (Makromonomer) enthält, das endständig eine ethylenisch ungesättigte Doppelbindung aufweist.
  5. Tintenzusammensetzung gemäß Anspruch 1, ferner umfassend einen Polymerisationsinitiator (c).
  6. Tintenzusammensetzung gemäß Anspruch 5, worin die polymerisierbare Verbindung (a) eine radikalisch polymerisierbare Verbindung ist und der Polymerisationsinitiator (c) ein Foto-Radikalbildner ist.
  7. Tintenzusammensetzung gemäß Anspruch 5, worin die polymerisierbare Verbindung (a) eine kationisch polymerisierbare Verbindung ist und der Polymerisationsinitiator (c) ein Foto-Säurebildner ist.
  8. Verwendung der Tintenzusammensetzung gemäß irgendeinem der Ansprüche 1 bis 7 für die Tintenstrahlaufzeichnung.
  9. Bedruckter Artikel/Drucksache, erhalten durch Härten der Tintenzusammensetzung gemäß irgendeinem der Ansprüche 1 bis 7.
  10. Tintenstrahlaufzeichnungsverfahren, umfassend:
    Ausstoßen der Tintenzusammensetzung gemäß irgendeinem der Ansprüche 1 bis 7 auf ein Aufzeichnungsmedium unter Verwendung eines Tintenstrahldruckers; und
    Bestrahlen der ausgestoßenen Tintenzusammensetzung mit aktiver Strahlung, um die Tintenzusammensetzung zu härten.
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